[go: up one dir, main page]

CN103281910B - Omega-3 concentrate - Google Patents

Omega-3 concentrate Download PDF

Info

Publication number
CN103281910B
CN103281910B CN201180062711.6A CN201180062711A CN103281910B CN 103281910 B CN103281910 B CN 103281910B CN 201180062711 A CN201180062711 A CN 201180062711A CN 103281910 B CN103281910 B CN 103281910B
Authority
CN
China
Prior art keywords
fatty acid
omega
mixture
ethyl ester
acid ethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201180062711.6A
Other languages
Chinese (zh)
Other versions
CN103281910A (en
Inventor
J·A·塞浦维达·雷耶斯
M·R·贝里奥斯·科尔内霍
M·A·富恩萨利达·迪亚兹
A·马考维特斯·罗杰斯
T·F·哈丁·格莱德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Golden Omega SA
Original Assignee
Golden Omega SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=45606887&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN103281910(B) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Golden Omega SA filed Critical Golden Omega SA
Publication of CN103281910A publication Critical patent/CN103281910A/en
Application granted granted Critical
Publication of CN103281910B publication Critical patent/CN103281910B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings or cooking oils
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/10—Production of fats or fatty oils from raw materials by extracting
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining
    • C11C1/10—Refining by distillation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/08—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with fatty acids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A simple, efficient method for obtaining a concentrate that comprises around 80% by weight -3 fatty acid ethyl esters from a composition of material that contains -3 fatty acid esters or free -3 fatty acids, which comprises the following steps: a) placing the composition of material in contact with at least 96% by weight ethanol an alkali and metal hydroxide at a temperature between 60 and 200 DEG C to form a liquid mixture that comprises fatty acid alkaline salts; b) cooling the liquid mixture to a temperature between 50 and -20 DEG C to form a solid phase and a liquid phase, and separating the liquid phase from the solid phase; c) placing the liquid phase separated in step b) in contact with an acid to form an acidified mixture with a water content of less than 10%, in which the mixture consists of a solid phase that comprises the alkali metal salt of the acid and a liquid phase that comprises -3 fatty acids; d) heating the mixture from step c) to 50 to 150 DEG C in the presence of an esterification catalyst to form a mixture that comprises -3 fatty acid ethyl esters; e) placing the mixture from step d) in contact with an alkali to form a neutralized mixture; f) distilling the neutralized mixture to obtain a distillate that comprises around 80% by weight -3 fatty acid ethyl esters.

Description

The concentrate of ω-3
Technical field
The present invention relates to a kind of efficiently simple method that composition of matter from the omega-fatty acid containing ester-formin or free fatty acid form obtains the omega-fatty acid concentrate containing the omega-fatty acid more than 80%.
Background technology
At present, ω-3 type long-chain gathers unrighted acid (such as octatecatrienoic acid (ALA; Alpha-linolenic acid), eicosapentaenoic acid (EPA) and DHA (DHA)) preventing artery sclerosis and cardiovascular disease, alleviation inflammatory symptoms and the validity postponed in tumor growth to be widely known by the people and to have had abundant record.The natural isomer of these omega-fatty acids has full cis-configuration, and their double bond is separated from one another by MU.When double bond is separated from one another by two or more singly-bound singly-bound, these double bonds are referred to as isolated double bond.The total daily dose of experts recommend omega-fatty acid is between 0.5g ~ 10g.Therefore, acquisition is increased day by day for the focusing on of omega-fatty acid concentrate added in food, nutriment and medicine.
Be rich in most the oil that one of source of omega-fatty acid (mainly EPA and DHA) is marine source, the such as fish oil of different plant species (such as sardine, scad, anchovy, salmon, cod and krill), marine microalgae (such as Phaeodactylum tricornutum (Phaeodactylum tricornotum), micro-Sphaerellopsis (Nannochloropsis sp.)); And be rich in the vegetable oil of ALA, such as linseed and cannabis seeds etc.The total content of EPA and DHA in the oil of marine source is generally 10 % by weight ~ 35 % by weight.In food and nutriment industry, refined fish oil is used to be used as the source of omega-fatty acid at present.Generally speaking, the method for refining of fish oil is the transformation of the classical method of refining of vegetable oil, can successfully reduce undesirable aroma and flavor specific to fish oil, thus make fish oil can be used for food and nutriment.Some are had to be disclosed in the documents such as United States Patent (USP) 4915876,4874629,4804555,4599143 and 4838997 in these methods.Except can successfully make fish oil be suitable for except human consumption, an advantage of known ichthyol smelting method is, these methods do not make the original concentration of the omega-fatty acid in these oil have obvious decline.
But the preparation of specific nutrient and medicine requires omega-fatty acid content higher than 60 % by weight, at least 70 % by weight, preferably higher than 80 % by weight product, use traditional oil refinement method obviously can not realize this point.
In the prior art, exist the much oil based on marine source manufacture omega-fatty acid content higher than 60 % by weight the method for concentrate.Because EPA and DHA found in marine oils is mainly the form (as in the situation of krill) of triglyceride and/or phosphatide, therefore most of method for concentration starts from and carries out chemical transesterification or enzymatic transesterification with alcohol (being generally ethanol) to these oil, or starts from and be hydrolyzed these oil to form the salt of aliphatic acid and the free acid from these salt with aqueous alkali.Then classification separating treatment is carried out to transesterification product or hydrolysate, to obtain required product.Usually, utilize single fractionation technique can not obtain the high concentrate of omega-fatty acid content, what therefore adopt is the combination of multiple technologies.
Forming compound with urea is one of fractionation technique the most frequently used when reclaiming EPA and/or the high concentrate of DHA content.
Urea has the characteristic forming solid composite or adduct with representative examples of saturated aliphatic organic compound.When in the composition of oil urea solution being added to the ester be derived from containing free acid or itself and monohydric alcohol, the crystalline composites containing the most saturated sour fraction or adduct will be formed.Then can remove this compound, leave the raffinate of more undersaturated acid.This composite algorithm is for free acid and methyl esters thereof or ethyl ester.
Then can carry out other steps of classification separation to raffinate, such as, if Breivik etc. is at US5, one or more molecular clock steps of the product containing the omega-fatty acid more than 80 % by weight disclosed in 945,318, can be obtained.
Other utilizing urea to carry out purifying raffinate are comprised by the technology used: Rubin etc. at patent US4,792, under the existence of acetone and other organic solvent, fractional crystallization is carried out to raffinate disclosed in 418; Lee at patent US6,664, in the post being filled with Ag-silica or Ag-aluminium oxide, high pressure liquid chromatography is carried out to raffinate disclosed in 405; With Wang at patent US5,679, utilize active carbon and hexane to process raffinate disclosed in 809.
But, relate to and utilize the method for urea to have multiple shortcomings and inconvenience.First one is that the rate of recovery of omega-fatty acid is low, be generally about 30%, this is because urea adds the adduct being bonded to saturated fatty acid also contain a large amount of omega-fatty acids, and the method that there is no economical and efficient at present reclaims unrighted acid from urea adduct, this makes the method very expensive, and needs in the mill to use complicated device and main equipment.Such as, for fish oil per ton, recyclable 60 kilograms ~ 80 kilograms final products, that is, be less than 8% (Breivik, Harald [2007], " Long Chain Omega-3Specialty Oils ", The Oily Press).
In addition, owing to using 1 ton ~ 3 tons ureas to marine oil per ton, a large amount of urea adducts formed form arduous challenge to its environmental treatment; In addition, also reported can produce in the method urethanes or these two kinds of strong carcinogens of methyl carbamate ( bl, Yurawecz MP [1999] " Ethyl carbamate formation during ureacomplexation for fractionation of fatty acids " .J.Am Oil Chem Soc76:537).
Although use the omega-fatty acid method of refining of urea to there is shortcoming and complicated, in the production of the current concentrate of omega-fatty acid content more than 80% in the whole world, these methods occupy more than 85%.
Do not using the classification separating step utilizing urea to produce in concentrated omega-fatty acid, disclosed method is few.One of them is by the method disclosed in Japanese patent application JP1982000131654 such as Kokubu, wherein, the fish oil after basic hydrolysis is cooled to 25 DEG C ~ 5 DEG C, to be settled out the soap shape thing of saturated fatty acid.Once isolate supernatant and add water to it, the organic solvents such as such as hexane, benzinum or benzene are namely utilized to extract it.Use the aqueous phase after mineral acid extraction to form aqueous phase and the organic phase containing the aliphatic acid formed to some extent, and utilize the organic solvents such as such as hexane, benzinum or benzene again to extract it, then by absorption and steam distillation or molecular clock, the organic phase after extracting is decoloured and taste removal operation.
Disclosed method only can manufacture EPA and DHA content is the concentrate of 60% ~ 70%, and this specific products being used for medicine and alimentary uses for preparation remains inadequate.In addition, the method adopts one or more extraction step utilizing hydro carbons or hydrocarbonylation solvent, and these hydro carbons or hydrocarbonylation solvent are being subject to very strict restriction for the maximum acceptable concentration in the product of human consumption.In the method manufacturing nutrition or medical components, be used in and (be less than 1mg/kg for the maximum acceptable concentration in the product of human consumption is extremely low, situation for hexane) organic solvent be inconvenient, because except inconvenience in other technologies and economically, remove to conform with the regulations the quality that these solvents can affect omega-fatty acid.
Morgan discloses a kind of method utilizing low temperature hydrolysis concentrated omega-fatty acid from fish oil in application WO2009/20406A1, and is not used in the organic solvent for the maximum acceptable concentration extremely low (being less than 1mg/kg) in the product of human consumption.In its description and unexposed method disclosed in it omega-fatty acid concentration that can reach, but embodiment shows, the concentration of the direct product of the method for the disclosure is between 46% ~ 65%.Although be apparent, the aliphatic acid of institute's enrichment in this inventor discloses " utilizing method of the present invention to obtain " poly-unrighted acid " can by such as distilling, fractional crystallization or form the known technologies such as urea compound and be further purified ".In example 2, the concentration of the omega-fatty acid of the product directly obtained by the method for this invention is 65%.The omega-fatty acid content of the product of experience recrystallization step (embodiment 3) is 75%, and this is still not enough for special nutrition and medical applications.
Other method by Cornieri etc. at patent US5,130, disclose in 061, wherein, after carrying out chemical transesterification to fish oil, the organic solvents such as such as hexane are used to extract this ester, after desolventizing, silica gel chromatograph separation and molecular clock are afterwards carried out to product, thus the content of acquisition EPA and DHA is lower than the concentrate of 70 % by weight.For improving concentration, the product through chromatographic isolation being dissolved in acetone and-40 DEG C of crystallizations, carrying out two step molecular clocks subsequently to obtained separation residue, thus the concentration of the ester of DHA can be made to reach 85 % by weight ~ 95 % by weight.The method also has the step using hexane, and this has inconvenience mentioned above.Chromatographic separation and purification step makes the method not have attraction economically, and its industrial implementation is also very complicated.In addition, the rate of recovery of omega-fatty acid is very low, is less than 30%.
Until 1986, Norwegian company's Jahres Fabrikker fish oil has manufactured the concentrate of EPA and DHA.The method comprises use sodium hydrate aqueous solution to be made fish oil saponification thus forms solid soap, uses solvent (normally methyl alcohol) to extract it afterwards.By the acidifying of methanol extraction thing, and isolate the free fatty (Breivik, Harald [2007] " Long Chain Omega-3Specialty Oils " The Oily Press) that EPA and DHA content are 50%.Molecular clock is carried out to this aliphatic acid, reaches the Cmax of 65%.
In the prior art, still there is not efficient following method: the method can obtain the omega-fatty acid concentrate of omega-fatty acid content more than 80%, and do not utilize urea or for the organic solvent that is restricted of maximum acceptable concentration in the product of human consumption to carry out classification separation.
For special medicine and nutritional applications importantly, in the concentrate of omega-fatty acid, these aliphatic acid are corresponding to having full cis-configuration and having the natural isomer according to double bond system spaced for isolated double bond distributed with methyl.
But in the process of concentrate manufacturing omega-fatty acid, also obtained trans isomer and conjugation isomer, wherein plural double bond by a singly-bound separately.
The method of the concentrate of the omega-fatty acid that the native configurations having disclosed manufacture aliphatic acid does not change, but never relate to the isomerization problem of double bond.Surprisingly, have been found that in the product obtained by method of the present invention, both trans isomer do not detected, the isomer with conjugated double bond also do not detected.
Therefore, the object of this invention is to provide a kind of organic solvent not utilizing urea or the maximum acceptable concentration in the product supplying human consumption to be restricted be suitable for human consumption to carry out classification separation thus to manufacture and there is the efficient of medicinal quality omega-fatty acid concentrate and simple method, wherein, based on the composition of matter of the omega-fatty acid containing ester-formin or free fatty acid form, described omega-fatty acid concentrate contains the omega-fatty acid more than 80%.
This object is realized by the method comprised the following steps:
A) at the temperature of 60 DEG C ~ 200 DEG C, the composition of matter of aliphatic acid containing ester-formin or free fatty acid form is contacted, to form the liquid mixture of the alkali metal salt comprising aliphatic acid with alkali metal hydroxide with the ethanol of at least 96 % by weight;
B) this liquid mixture is cooled to the temperature of 50 DEG C ~-20 DEG C to form solid phase and liquid phase, and this liquid phase is separated with this solid phase;
C) make step b) in isolated liquid phase contact with acid with is formed water content lower than 10% acidifying mixture, wherein said mixture is made up of the solid phase comprising sour alkali metal salt and the liquid phase that comprises omega-fatty acid, and by this two-phase laminated flow;
D) under the existence of esterification catalyst, in 50 DEG C ~ 150 DEG C heating steps c) liquid phase, to form the mixture comprising omega-fatty acid ethyl ester;
E) make steps d) mixture contact with alkali, to form the mixture of the neutralization comprising omega-fatty acid ethyl ester, and isolate the ethyl ester of the mixture of this neutralization;
F) distilation steps e) ethyl ester, to obtain the distillation of the omega-fatty acid ethyl ester comprised more than 80 % by weight.
Detailed description of the invention
For the method described in present patent application, the raw material used is any composition of matter of the omega-fatty acid containing esterification, the form of the omega-fatty acid of described esterification is form of triglycerides, phospholipid form or other forms, the such as raw material of following form: the oil of animal origin or fat, the thick refining of such as different plant species (such as sardine, scad, anchovy, salmon, cod, krill) or refined fish oil; Marine microalgae (such as Phaeodactylum tricornutum, micro-Sphaerellopsis); The oil of plant origin or fat, the such as vegetable oil of linseed, cannabis seeds; The oil of marine source or the mixture of fat and vegetable oil; Or the form of the product of the monoester form of free fatty, separate sources or commercially available approach.Usually, the total content of omega-fatty acid (EPA and DHA) in fish oil is 10 % by weight ~ 35 % by weight, and in vegetable oil (ALA), its excursion is very large, can reach close to 50%, as in linseed oil.In the present invention, word " oil " also comprises the fat containing omega-fatty acid.Difference between oil and fat is, at room temperature the former is liquid, and the latter is solid.The lipid extracted from various marine microalgae is at room temperature solid, and can containing the omega-fatty acid of 5% ~ 30%.What also can be used as raw material of the present invention is from insect, insect larvae and for manufacturing the lipid extracted the plant of long-chain omega-fatty acid and genetic modification.
For implementing the present invention, first with alkali metal hydroxide, saponification or neutralization procedure are carried out to the raw material containing omega-fatty acid, to form the reactant mixture comprising fatty acid alkali metal salt.For this reason, at the 60 DEG C ~ temperature of 200 DEG C, preferably 120 DEG C and under low pressure, make described raw material and water content be no more than 4 % by weight, be preferably less than the ethanol (being preferably absolute ethyl alcohol) of 1 % by weight and alkali metal hydroxide (preferred NaOH) or alkali metal hydroxide (preferred NaOH) solution and contact.If use sodium hydroxide solution, then sodium hydroxide solution be selected from by the sodium hydrate aqueous solution more than 40 % by weight and lower than 50 % by weight the group that forms of NaOH ethanolic solution.At such a temperature, the saponification of raw material or the reaction time of neutralization only need a few minutes, and this has and can carry out the additional advantage of reacting with simple and continuous print process.The amount of the ethanol used in reaction can be 0.5kg/kg raw material ~ 10kg/kg raw material, be preferably 1kg/kg raw material ~ 6kg/kg raw material, and the amount of alkali metal hydroxide used in reaction is equal to or greater than 90 % by mole of saponification index institute indicating value, preferably greater than 100%, in the situation using NaOH, this represents that at least 0.712g NaOH/kilogram raw material is multiplied by the saponification index of raw material.This reaction can be carried out in batches or carry out continuously in other types container conventional in vibration container or tubular container or when making oil & fat saponification.When used raw material be rough or the fish oil of refining (its be used alone or with vegetable oil conbined usage) time, purifying can be carried out, to remove the persistence organic pollutant (POC) that may exist to this raw material or fish oil that is rough or refining alternatively by methods known in the art.POC is the toxic chemical product accumulated in the adipose tissue of live organism.In different fish species, find the POC of relative high levels, and then in the food manufactured from these species and oil, have also discovered the POC of relative high levels.POC comprise pesticide, industrial chemistry product (as Polychlorinated biphenyls), industrial process accessory substance (as bioxin and furans).Similarly, POC removal step can be adopted to product of the present invention.
At the end of this step, make reactant mixture be cooled to 50 DEG C ~-20 DEG C, the temperature of preferably to 50 DEG C ~ 0 DEG C, thus produce the partly precipitated of alkali metal salt or the sodium salt formed in course of reaction, this precipitation comprises the salt of saturated fatty acid.The cooling of reactant mixture can be carried out in batches or carry out continuously in following container, and described container is wall cold and/or vaporation-type vibration container, and it is equipped with any mechnical oscillator, such as flat-blade turbine or anchor agitator; Or tubular container, it preferably utilizes scraped wall agitator to vibrate; Or be usually used in the container of the other types in the crystallization of oil & fat.
Then, by mechanical means, such as centrifugal or filter, preferably by vacuum filtration or press filtration, the liquid phase separation of the solid phase making the alkali metal salt comprising precipitation and the mixture of cooling obtained.Optionally, again can cool the liquid phase of liquid phase or cooling evaporation and concentration in advance, until be settled out more solid, then as described, liquid phase is separated with the solid be settled out, afterwards following acidification step be carried out to liquid phase.
Use acid or use acid to carry out acidification step with the mixture (preferably using sulfuric acid) of alcohol to isolated liquid phase, thus obtain the acidifying mixture comprising liquid phase and solid phase, described liquid phase comprises free omega-fatty acid, and described solid phase contains alkali metal salt or the sodium salt of this acid.Acidifying mixture comprises and is less than 10 % by weight, be preferably less than the water of 5 % by weight, and this makes it possible to the solid producing liquid phase and be suspended in described liquid phase.In acid with the mixture of alcohol, the percentage of acid is less than 50 % by weight.If use sulfuric acid, then recommendable, preferably preparation lower than 20% and temperature lower than 20 DEG C, preferably lower than the ethanolic solution of 10 DEG C, to avoid the formation of the hydrosulphate (ethanol sulfate) of ethanol.The amount of the acid used or the amount of acid mixed with ethanol depend on cooling step after isolated liquid phase total alkaline, and use the slightly excessive amount higher than total alkaline stoichiometric number 1% ~ 10%.Preferably, the alkali metal salt formed in acidification step or sodium salt that are in fact insoluble to acidifying mixture are separated with described acidifying mixture, preferably by centrifugal, filter or decant be separated, to obtain the supernatant liquid comprising omega-fatty acid.
Acidifying mixture or supernatant liquid are heated to the temperature of 50 DEG C ~ 150 DEG C, to make aliphatic acid and existing ethanol synthesis, thus form the esterification mixture comprising the ethyl ester of these aliphatic acid.In esterification process, utilizing sulfuric acid to perform in the situation of acidification step, existing same sulfuric acid also serves as the catalyst of esterification.But, if needed, or can heat before heating acidifying mixture or supernatant liquid in its process, add more sulfuric acid or other esterification catalysts (as p-methyl benzenesulfonic acid) wherein.Similarly, using the acid beyond sulfuric acid (example hydrochloric acid) to perform in the situation of acidification step, or must heat before heating acidifying mixture or supernatant liquid in its process and add esterification catalyst wherein.Easily, in step before, the use of water is made to minimize, because its esterification affecting aliphatic acid transforms.
Then, the aqueous solution of described esterification mixture and alkali or ethanolic solution are contacted, with form neutralization or the mixture of alkalescence, wherein said alkali is selected from the group be made up of alkali-metal oxide, hydroxide and carbonate and ammonia and ammonium hydroxide, preferred NaOH.Afterwards, the technology (it will illustrate in an embodiment) easily expected by those of ordinary skill in the art reclaims omega-fatty acid ethyl ester from the mixture of neutralization.From neutralization or alkalescence mixture to reclaim an alternative of ethyl ester as follows: the ethanolic solution of NaOH is contacted with esterification mixture, thus form mixture that is that neutralize or alkalescence, solvent in evaporate this neutralization or alkalescence mixture is to form residue, this residue is made up of the light phase comprising omega-fatty acid ethyl ester and the heavy phase that comprises inorganic salts or glycerine, and by decant or centrifugally make this two-phase laminated flow.Optionally, by the light phase of solution washing of water or salt.
Another alternative is: esterification mixture is contacted with sodium hydrate aqueous solution, and to form the mixture of neutralization, the mixture of this neutralization contains the light phase comprising omega-fatty acid ethyl ester and the heavy phase comprising inorganic salts, water, ethanol or glycerine.By decant or centrifugally make these be separated.Optionally, by the light phase of solution washing of water or salt.
Then, comprise the light of omega-fatty acid ethyl ester carry out one or more vacuum distillation step mutually, to obtain the concentrate of the omega-fatty acid ethyl ester of content more than 80%, usually more than 90% to isolated in the mixture from neutralization.Distilation steps preferably the temperature of 100 DEG C ~ 250 DEG C and lower than the pressure of 1 millibar under carry out in molecular still or short-distance distiller.When raw material is made up of fish oil, method of the present invention usually can obtain EPA and add the omega-fatty acid concentrate of DHA more than 80%.
Method of the present invention has following additional advantage: if use fish oil as raw material, have the omega-fatty acid high-recovery more than 30%, usually more than 40%, this is surprising high level compared with the method for prior art for this.In addition, method of the present invention can process the low raw material of omega-fatty acid content, and without detriment to the high efficiency of the method.On the contrary, the commercial run of the manufacture omega-fatty acid concentrate of urea or molecular clock is used then to require that raw material has the omega-fatty acid of the high-load more than 28% usually.In addition, all accessory substances of the step of method of the present invention have direct industrial use, namely to the efficiency utilization of renewable raw materials.
Surprisingly, as in embodiment confirm, in disclosed this method, undesirable compound do not detected, the sulfating product (such as dithyl sulfate) of such as trans-fatty acid or ethanol, in addition, there are not conjugated bonds in omega-fatty acid ethyl ester.
Embodiment
Method disclosed in " Official methods and recommended practices of the AOCS " (the 6th edition) is used to analyze omega-fatty acid content in bed blending product and information.
Embodiment 1
Take pilchard oil as the concentrate that initiation material obtains omega-fatty acid ethyl ester.
By the ethanol of 276g NaOH, 6kg99.2% and 2kg pilchard oil (SouthPacific Korp, omega-fatty acid content is 32.9%; EPA is 16.8%, DHA is 11.3%) rise in pressure reactor at the Parr20 with agitator and mix.Under the stirring of 250rpm, mixture is heated 5 minutes at 120 DEG C, be then cooled to 35 DEG C at 100 rpm.
Mylar carries out vacuum filtration to the mixture of cooling in Buchner funnel, and obtains the first filtrate.Use the filter cake collected in 6,000g ethanol washing filter, thus reclaim the second filtrate, it is mixed with the first filtrate.
At 0 DEG C, the ethanol solution of sulfuric acid of filtrate and 1,700g10% is mixed, and form the acidifying mixture being dispersed with insoluble solid.Centrifugation goes out described solid, obtains settled solution.
Settled solution is loaded in the reactor being equipped with agitator, external condensation device and vacuum connection tube.At room temperature distill 70% of heap(ed) capacity.Then, add the ethanol solution of sulfuric acid of 25g20%, be heated to 76 DEG C and keep 30 minutes, being then cooled to 20 DEG C.Then, add the NaOH ethanolic solution of 150g8%, under the pressure of 10 millibars at the most, evaporate existing all ethanol afterwards.Decant final residual thing 5 minutes, to isolate about 205g heavy phase.Make to wash light phase with water, reclaim and obtain 1,056g ethyl ester.
Ethyl ester is loaded in short-distance distiller (UIC board, model KDL5) and also distill in two steps.In a first step, under the vacuum level of the jacket temperature of 85 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.02 millibar, distillation loads thing.Collect residue, and under the vacuum level of the jacket temperature of 110 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.01 millibar, distill this residue in second step, collect 451g distillation, its omega-fatty acid ethyl ester content is 97.1%; EPA-EE is 45.2% and DHA-EE is 37.3%.
The overall recovery of omega-fatty acid is 60%.
Embodiment 2
The concentrate of omega-fatty acid ethyl ester is obtained from scad oil.
By the ethanol of 281g NaOH, 11kg99.2% and 2kg scad oil (SouthPacific Korp, omega-fatty acid content is 38.5%; EPA12.5%, DHA20.4%) to rise in pressure reactor at the Parr20 with agitator and mix.Under the stirring of 250rpm, mixture is heated 5 minutes at 120 DEG C, then under the stirring of 100rpm, be cooled to 5 DEG C.
Mylar carries out vacuum filtration to the mixture of cooling in Buchner funnel, and obtains the first filtrate.Use the filter cake collected in 3,000g ethanol washing filter, thus reclaim the second filtrate, it is mixed with the first filtrate.
Filtrate is mixed with the HCl (using 370g ethanol to dissolve in advance) of 370g36%, and forms the acidifying mixture being dispersed with insoluble solid.Centrifugation goes out described solid, obtains settled solution.
In the reactor being equipped with agitator, external condensation device and vacuum connection tube, this settled solution is mixed with 6g p-methyl benzenesulfonic acid.At room temperature distill 70% of heap(ed) capacity.Then, add the sodium hydroxide solution of 20g50%, under the pressure of 10 millibars at the most, evaporate existing all ethanol afterwards.Decant residue is to be separated heavy phase.Use the aqueous sodium persulfate solution of 2 % by weight to wash light phase, and recovery obtain 977g ethyl ester.
Ethyl ester is loaded in short-distance distiller (UIC board, model KDL5) and also distill in two steps.In a first step, under the vacuum level of the jacket temperature of 84 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.02 millibar, distillation loads thing.Collect residue, and under the vacuum level of the jacket temperature of 114 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.01 millibar, distill this residue in second step, collect 508g distillation, its omega-fatty acid ethyl ester content is 92.6%; EPA-EE is 30.2% and DHA-EE is 52.3%.
The overall recovery of omega-fatty acid is 56%.
Embodiment 3
The concentrate of omega-fatty acid ethyl ester is obtained from linseed oil.
By the NaOH of 560g50%, the ethanol of 10kg99.2% and 2kg linseed oil (Terrasol, omega-fatty acid content is 51.7%; ALA is 51.7%) rise in pressure reactor at the Parr20 with agitator and mix.Under the stirring of 250rpm, mixture is heated 25 minutes at 80 DEG C, be then cooled to 0 DEG C at 100 rpm.
Mylar carries out vacuum filtration to the mixture of cooling in Buchner funnel, and obtains the first filtrate.Use the filter cake collected in 2,000g ethanol washing filter, thus reclaim the second filtrate, it is mixed with the first filtrate.
Filtrate is mixed with the 180g concentrated sulfuric acid, and forms the acidifying mixture being dispersed with insoluble solid.
In the reactor being equipped with agitator, external condensation device and vacuum connection tube, settled solution is mixed with 7g p-methyl benzenesulfonic acid.At room temperature distill 70% of heap(ed) capacity.Then, filtering and concentrating mixture is to obtain clean product under stress, adds the sodium hydroxide solution of 20g50% wherein, evaporates existing all ethanol afterwards under the pressure of 10 millibars at the most.Decant residue is also separated heavy phase.Wash light phase with water, reclaim and obtain 871g ethyl ester.
Ethyl ester is loaded in short-distance distiller (UIC board, model KDL5) and also distill in two steps.In a first step, under the vacuum level of the jacket temperature of 72 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.02 millibar, distillation loads thing.Collect residue, and under the vacuum level of the jacket temperature of 95 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.01 millibar, distill this residue in second step, collect 580g distillation, its omega-fatty acid ethyl ester content is 89.6%; ALA ethyl ester is 89.6%.
The overall recovery of omega-fatty acid is 45%.
Embodiment 4
The concentrate of omega-fatty acid ethyl ester is obtained from krill oil.
Use omega-fatty acid content is the krill oil of 27.5% (EPA is 9.5% and DHA is 15.4%), repeats the test of embodiment 1.
Obtain the final distillation of 354g, its omega-fatty acid ethyl ester content is 92.3%; EPA-EE is 28.3% and DHA-EE is 56.6%.
The overall recovery of omega-fatty acid is 54%.
Embodiment 5
The concentrate of omega-fatty acid ethyl ester is obtained from the mixture of linseed oil and pilchard oil.
Use the linseed oil of 500g embodiment 3 and the pilchard oil of 1,500g embodiment 1, repeat the test of embodiment 1.
Obtain the final distillation of 514g, its omega-fatty acid ethyl ester content is 88.9%; ALA ethyl ester is 29.8%; EPA-EE is 26.3% and DHA-EE is 17.1%.
The overall recovery of omega-fatty acid is 47%.
Embodiment 6
The concentrate of omega-fatty acid ethyl ester is obtained from the aliphatic acid of fish.
By the free fatty of the ethanol of 280g NaOH, 10kg99.2% and 2kg fish (SouthPacific Korp, omega-fatty acid content is 26.8%; EPA is 13.6% and DHA is 9.2%) rise in pressure reactor at the Parr20 with agitator and mix.Under the stirring of 250rpm, mixture is heated 15 minutes at 60 DEG C, then under the stirring of 100rpm, be cooled to 25 DEG C.
Mylar carries out vacuum filtration to the mixture of cooling in Buchner funnel, and reclaims the first filtrate.Use the filter cake collected in 3,000g ethanol washing filter, thus reclaim the second filtrate, it is mixed with the first filtrate.
Filtrate is mixed with the HCl (using 400g ethanol to dissolve in advance) of 400g36%, and forms the acidifying mixture being dispersed with insoluble solid.Isolate described solid by pressure filtration, obtain settled solution.
In the reactor being equipped with agitator, external condensation device and vacuum connection tube, this settled solution is mixed with 5g p-methyl benzenesulfonic acid.At room temperature distill 70% of heap(ed) capacity.Then, add the NaOH ethanolic solution of 100g8%, under the pressure of 10 millibars at the most, evaporate existing all ethanol afterwards.Make the residue washing distillation with water.Recovery obtains 820g ethyl ester.
Ethyl ester is loaded in short-distance distiller (UIC board, model KDL5) and also distill in two steps.In a first step, under the vacuum level of the jacket temperature of 77 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.02 millibar, distillation loads thing.Collect residue, and under the vacuum level of the jacket temperature of 114 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.01 millibar, distill this residue in second step, collect 409g distillation, its omega-fatty acid ethyl ester content is 87.0%; EPA-EE is 40.5% and DHA-EE is 33.5%.
The overall recovery of omega-fatty acid is 60%.
Embodiment 7
The concentrate of omega-fatty acid ethyl ester is obtained from the fish oil that omega-fatty acid content is low.
Use omega-fatty acid content is the rough low-quality fish oil (acid number is the sample of 19mg KOH/g) of 23.5% (EPA is 12.5% and DHA is 8.4%), repeats the test of embodiment 1.
Obtain the final distillation of 235g, its omega-fatty acid ethyl ester content is 90.3%; EPA-EE is 55.1% and DHA-EE is 27.5%.
The overall recovery of omega-fatty acid is 42%.
Embodiment 8
The concentrate of omega-fatty acid ethyl ester is obtained from pilchard oil.
By the ethanol of 280g NaOH, 6kg99.2% and 2kg pilchard oil (SouthPacific Korp, omega-fatty acid content is 32.9%; EPA is 16.8%, DHA is 11.3%) rise in pressure reactor at the Parr20 with agitator and mix.Under the stirring of 250rpm, mixture is heated 5 minutes at 120 DEG C, then under the stirring of 100rpm, be cooled to 48 DEG C.
Mylar carries out vacuum filtration to the mixture of cooling in Buchner funnel, and reclaims the first filtrate.Use the filter cake collected in 2,000g ethanol washing filter, thus reclaim the second filtrate, it is mixed with the first filtrate.By this filtrate mixture evaporation and concentration to mostly being most 50% of heap(ed) capacity, to obtain residue, residue is cooled to 0 DEG C.Filtration residue also obtains the 3rd filtrate.
At 0 DEG C, the ethanol solution of sulfuric acid of the 3rd filtrate and 1,200g10% is mixed, and form the acidifying mixture being dispersed with insoluble solid.Centrifugation goes out described solid, obtains settled solution.
Settled solution is loaded in the reactor being equipped with agitator, external condensation device and vacuum connection tube.At room temperature distill 50% of heap(ed) capacity.Then, add the ethanol solution of sulfuric acid of 25g20%, it is heated 30 minutes at 78 DEG C and be cooled to 20 DEG C.Then, add the NaOH ethanolic solution of 8%, under the pressure of 10 millibars at the most, evaporate existing all ethanol afterwards.Decant final residual thing, and isolate heavy phase.Make to wash light phase with water, reclaim and obtain 556g ethyl ester.
Ethyl ester is loaded in short-distance distiller (UIC board, model KDL5) and also distill in two steps.In a first step, under the vacuum level of the jacket temperature of 88 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.02 millibar, distillation loads thing.Collect residue, and under the vacuum level of the jacket temperature of 115 DEG C, the internal condensation actuator temperature of 5 DEG C and 0.01 millibar, distill this residue in the second step.Obtaining omega-fatty acid ethyl ester content is the concentrate of 99.7%.
Embodiment 9
To the analysis of the trans-fatty acid in omega-fatty acid ethyl ester concentrate.
Gas-chromatography is used to analyze the content of trans fatty acids in the omega-fatty acid ethyl ester concentrate in the test of embodiment 1 ~ 8.
Trans-fatty acid is not detected in the omega-fatty acid ethyl ester concentrate sample of embodiments of the invention.
Embodiment 10
To the analysis of the conjugated fatty acid in omega-fatty acid ethyl ester concentrate.
Ultraviolet absorption spectroscopy is used to analyze the conjugated fatty acid content in the omega-fatty acid ethyl ester concentrate in the test of embodiment 1 ~ 8.
Conjugated fatty acid is not detected in the omega-fatty acid ethyl ester concentrate sample of embodiments of the invention.
Embodiment 11
To the analysis of the dithyl sulfate (DES) in omega-fatty acid ethyl ester concentrate.
By internal standard method for gas chromatography, the DES content in the omega-fatty acid ethyl ester concentrate in the test of embodiment 1 ~ 8 is analyzed.
DES is not detected in omega-fatty acid ethyl ester concentrate sample in an embodiment of the present invention.
Embodiment 12
Determine free acidity, peroxide value and Anisidine index.
The international procedure adopting AOCS to disclose, determines the value of the free acidity of the omega-fatty acid ethyl ester concentrate in the test of embodiment 1 ~ 8, peroxide value and Anisidine index.
For all omega-fatty acid ethyl ester concentrates, free acidity is lower than the 1mg KOH/g of sample.
For all omega-fatty acid ethyl ester concentrates, peroxide value is lower than the 3meq/kg of sample.
For all omega-fatty acid ethyl ester concentrates, anisidine value is lower than 15.

Claims (5)

1. obtain a method for the omega-fatty acid ethyl ester concentrate of the omega-fatty acid ethyl ester comprised more than 80 % by weight from fish oil, it is characterized in that it is made up of following steps:
A) at the temperature of 60 DEG C ~ 200 DEG C, make described fish oil and alkali metal hydroxide with at least 96 % by weight ethanol contact, to form the liquid mixture comprising fatty acid alkali metal salt;
B) formed liquid mixture is cooled to the temperature of 50 DEG C ~-20 DEG C to form solid phase and liquid phase, and described liquid phase is separated with described solid phase;
C) make step b) in isolated liquid phase contact with acid with formed water content lower than 10% acidifying mixture, wherein said mixture is made up of with the liquid phase that comprises omega-fatty acid the solid phase of the alkali metal salt comprising described acid;
D) described liquid phase is separated with described solid phase;
E) under the existence of esterification catalyst, in 50 DEG C ~ 150 DEG C isolated liquid phases of heating, to form the mixture comprising omega-fatty acid ethyl ester;
F) make step e) mixture contact with alkali, to form the mixture of the neutralization comprising omega-fatty acid ethyl ester, and isolate the ethyl ester of the mixture of this neutralization;
G) distilation steps f) ethyl ester, to obtain the distillation of the omega-fatty acid ethyl ester comprised more than 80 % by weight.
2. the method for claim 1, is characterized in that, step a) in described temperature be 90 DEG C ~ 150 DEG C.
3. method as claimed in claim 2, is characterized in that, step a) in described temperature be 120 DEG C.
4. the method for claim 1, is characterized in that, step b) in described temperature be 50 DEG C ~ 0 DEG C.
5. the method for claim 1, is characterized in that, step c) in described acid be selected from the group be made up of sulfuric acid and hydrochloric acid.
CN201180062711.6A 2010-12-27 2011-12-25 Omega-3 concentrate Active CN103281910B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CL2010001587A CL2010001587A1 (en) 2010-12-27 2010-12-27 Process for preparing a concentrate of omega-3 fatty acid ethyl esters comprising over 80% by weight of said esters in cis configuration and their double bonds separated by a methylene unit.
CL1587-2010 2010-12-27
PCT/CL2011/000082 WO2012088620A2 (en) 2010-12-27 2011-12-25 Omega‑3 concentrate

Publications (2)

Publication Number Publication Date
CN103281910A CN103281910A (en) 2013-09-04
CN103281910B true CN103281910B (en) 2015-04-15

Family

ID=45606887

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180062711.6A Active CN103281910B (en) 2010-12-27 2011-12-25 Omega-3 concentrate

Country Status (14)

Country Link
US (1) US8957231B2 (en)
EP (1) EP2659780B2 (en)
JP (1) JP5861968B2 (en)
KR (1) KR101506412B1 (en)
CN (1) CN103281910B (en)
AU (1) AU2011350073C1 (en)
CA (1) CA2822314C (en)
CL (1) CL2010001587A1 (en)
CO (1) CO6710941A2 (en)
DK (1) DK2659780T3 (en)
ES (1) ES2716817T5 (en)
MA (1) MA34715B1 (en)
PE (1) PE20140810A1 (en)
WO (1) WO2012088620A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI821982B (en) * 2018-06-21 2023-11-11 美商努賽德營養美國股份有限公司 Dha enriched polyunsaturated fatty acid compositions

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014054435A1 (en) * 2012-10-01 2014-04-10 日清ファルマ株式会社 Method for producing composition containing higher unsaturated fatty acid alkyl ester
ITMI20121681A1 (en) * 2012-10-08 2014-04-09 Milanotrading Srl METHOD OF PRODUCTION OF ETHYLIC ESTERS OF ACID FAT POLYINSATURES AND THEIR USE IN FORMULATIONS FOR ORAL USE IN MAN
US9409851B2 (en) * 2014-04-07 2016-08-09 Epax Norway As Long chain monounsaturated fatty acid composition and method for the production thereof
PE20180456A1 (en) 2015-05-13 2018-03-05 Epax Norway As VERY LONG CHAIN POLYINSATURATED FATTY ACIDS FROM NATURAL OILS
WO2017038860A1 (en) 2015-08-31 2017-03-09 日本水産株式会社 Free polyunsaturated fatty acid-containing composition and manufacturing method therefor
JP6967334B2 (en) * 2015-12-21 2021-11-17 備前化成株式会社 Compositions Containing Polyunsaturated Fatty Acid Esters
EP3586640A1 (en) 2018-06-21 2020-01-01 Nuseed Pty Ltd Dha enriched polyunsaturated fatty acid compositions
EP3586642A1 (en) * 2018-06-21 2020-01-01 Nuseed Pty Ltd Ala enriched polyunsaturated fatty acid compositions
AU2021214454A1 (en) * 2020-01-30 2022-09-08 Silicycle Inc. Process of producing magnesium salts of PUFAs and composition containing same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1036008A (en) * 1988-03-26 1989-10-04 山东省海洋药物科学研究所 The method for separating and preparing of timnodonic acid and docosahexenoic acid and ester class thereof
US5679809A (en) * 1994-05-09 1997-10-21 Nestec S.A. Concentrate of polyunsaturated fatty acid ethyl esters and preparation thereof
CN1204638A (en) * 1997-07-02 1999-01-13 湖南天海林实业股份有限公司 Preparation of docosahexenoic acid and esterification technology
EP1211304A2 (en) * 2000-11-30 2002-06-05 Sepu Fine Chem Co., Ltd. Method for isolating high-purified unsaturated fatty acids using crystallization

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57149400A (en) * 1981-03-12 1982-09-14 Kureha Chemical Ind Co Ltd Manufacture of high purity long chain highly unsaturated fatty acid ester
DE3227669C1 (en) 1982-07-23 1983-07-07 Hermann Dr. 4400 Münster Stage Process and plant for deodorising and / or deacidifying edible oils, fats and esters
JPS5921641A (en) 1982-07-28 1984-02-03 Kureha Chem Ind Co Ltd Method for concentrating and separating eicosapentaenoic acid and docosahexaenoic acid
GB8314496D0 (en) 1983-05-25 1983-06-29 Unilever Plc Treating triglyceride oil
US4792418A (en) 1985-08-14 1988-12-20 Century Laboratories, Inc. Method of extraction and purification of polyunsaturated fatty acids from natural sources
US4804555A (en) 1986-10-21 1989-02-14 General Mills, Inc. Physical process for simultaneous deodorization and cholesterol reduction of fats and oils
IT1205043B (en) 1987-05-28 1989-03-10 Innova Di Ridolfi Flora & C S PROCEDURE FOR THE EXTRACTION OF POLYUNSATURATED FATTY ACID ESTERS FROM FISH OILS AND PHARMACEUTICAL AND DIETARY COMPOSITIONS CONTAINING SUCH ESTERS
US4915876A (en) 1987-07-20 1990-04-10 General Mills, Inc. Process for the deodorization and stabilization of polyunsaturated oils
US4874629A (en) 1988-05-02 1989-10-17 Chang Stephen S Purification of fish oil
GB8819110D0 (en) * 1988-08-11 1988-09-14 Norsk Hydro As Antihypertensive drug & method for production
GB9404483D0 (en) 1994-03-08 1994-04-20 Norsk Hydro As Refining marine oil compositions
IT1274734B (en) 1994-08-25 1997-07-24 Prospa Bv PHARMACEUTICAL COMPOSITIONS CONTAINING POLYUNSATURATED FATTY ACIDS, THEIR ESTERS OR SALTS, WITH VITAMINS OR ANTIOXIDANT PROVITAMINS
KR20040086004A (en) * 2003-03-27 2004-10-08 임호빈 High cell density fermentation of Chlorella sp. containing w-3 fatty acid by heterotrophic fed-batch culture
ITMI20051560A1 (en) * 2005-08-10 2007-02-11 Tiberio Bruzzese COMPOSITION OF N-3 FATTY ACIDS WITH HIGH CONCENTRATION OF EPA AND E-O DHA AND CONTAINING N-6 FATTY ACIDS
FR2894772B1 (en) * 2005-12-20 2008-03-14 Pierre Fabre Medicament Sa DHA ENRICHMENT PROCESS
WO2009020406A1 (en) * 2007-08-07 2009-02-12 Granate Seed Limited Methods of making lipid substances, lipid substances made thereby and uses thereof
CL2009001343A1 (en) * 2009-06-02 2009-07-10 Golden Omega S A Process of obtaining concentrated esters of epa and dha from marine oil, which includes adding to the alkali oil and water at less than 100 degrees Celsius, adding solvent, separating refining phase, adding acid, separating the non-aqueous phase and adding alcohol and a catalyst at less than 150 degrees Celsius, desolventilize and distill.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1036008A (en) * 1988-03-26 1989-10-04 山东省海洋药物科学研究所 The method for separating and preparing of timnodonic acid and docosahexenoic acid and ester class thereof
US5679809A (en) * 1994-05-09 1997-10-21 Nestec S.A. Concentrate of polyunsaturated fatty acid ethyl esters and preparation thereof
CN1204638A (en) * 1997-07-02 1999-01-13 湖南天海林实业股份有限公司 Preparation of docosahexenoic acid and esterification technology
EP1211304A2 (en) * 2000-11-30 2002-06-05 Sepu Fine Chem Co., Ltd. Method for isolating high-purified unsaturated fatty acids using crystallization

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI821982B (en) * 2018-06-21 2023-11-11 美商努賽德營養美國股份有限公司 Dha enriched polyunsaturated fatty acid compositions

Also Published As

Publication number Publication date
EP2659780B2 (en) 2021-06-23
KR101506412B1 (en) 2015-04-07
MA34715B1 (en) 2013-12-03
JP5861968B2 (en) 2016-02-16
CL2010001587A1 (en) 2013-01-11
CA2822314C (en) 2016-01-05
PE20140810A1 (en) 2014-07-11
US8957231B2 (en) 2015-02-17
WO2012088620A3 (en) 2012-09-13
JP2013545857A (en) 2013-12-26
AU2011350073C1 (en) 2015-01-29
KR20130084302A (en) 2013-07-24
EP2659780B1 (en) 2019-02-13
WO2012088620A2 (en) 2012-07-05
CN103281910A (en) 2013-09-04
US20130267600A1 (en) 2013-10-10
CO6710941A2 (en) 2013-07-15
ES2716817T5 (en) 2021-12-29
EP2659780A2 (en) 2013-11-06
DK2659780T3 (en) 2019-04-29
AU2011350073B2 (en) 2014-07-17
CA2822314A1 (en) 2012-07-05
AU2011350073A1 (en) 2013-05-23
ES2716817T3 (en) 2019-06-17

Similar Documents

Publication Publication Date Title
CN103281910B (en) Omega-3 concentrate
KR102678363B1 (en) Very long chain polyunsaturated fatty acids from natural oils
JP6684932B2 (en) Method for producing composition containing highly unsaturated fatty acid alkyl ester
US5106542A (en) Process for the continuous fractionation of a mixture of fatty acids
CN103804337B (en) The technique that multi-stage countercurrent liquid-liquid extraction method extracts vitamin E and Squalene
JPH0225447A (en) Production of highly unsaturated fatty acids
JPH0159318B2 (en)
JPS649977B2 (en)
Lembke Production techniques for omega-3 concentrates
Liang et al. Fractionation of squid visceral oil ethyl esters by short-path distillation
CN101544557A (en) Coupling rectification system and application thereof in purifying EPA, DPA, and DHA in seal oil
CN107216252A (en) A kind of preparation method of high content Omega-3 fatty-acid ethyl esters
CN109438227B (en) Production method of omega-3 polyenoic fatty acid ethyl ester
JP2022525570A (en) Fish oil cholesterol
Pando et al. Concentrating n-3 fatty acids from crude and refined commercial salmon oil
JPH03279385A (en) Separation of sesamins
CN1089366C (en) Process for obtaining oryzanol
CN1091106C (en) Supercritical fluid extraction process for extracting concentrated natural vitamin E
US20230365615A1 (en) Process of obtaining cholesterol present in fish oil
CN108477309A (en) A kind of phosphatide type catalpic acid fat or oil composition and its preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant